US8420425B2 - Method for producing a group III nitride semiconductor light-emitting device - Google Patents

Method for producing a group III nitride semiconductor light-emitting device Download PDF

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US8420425B2
US8420425B2 US13/481,386 US201213481386A US8420425B2 US 8420425 B2 US8420425 B2 US 8420425B2 US 201213481386 A US201213481386 A US 201213481386A US 8420425 B2 US8420425 B2 US 8420425B2
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nitride semiconductor
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US20120309124A1 (en
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Koji Okuno
Atsushi Miyazaki
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Toyoda Gosei Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0062—Processes for devices with an active region comprising only III-V compounds
    • H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds

Definitions

  • the present invention relates to a method for producing a Group III nitride semiconductor light-emitting device, and more particularly, to a method for forming a p cladding layer.
  • a p cladding layer is provided to improve emission performance by confining electrons in a light-emitting layer of a Group III nitride semiconductor light-emitting device.
  • p-AlGaN having large bandgap energy is used as a p cladding layer.
  • p-AlGaN needs to be grown at a low temperature to reduce thermal damage to the light-emitting layer, resulting in degradation of crystal quality. Therefore, a p-AlGaN/p-InGaN or p-AlGaN/p-GaN superlattice structure is used to suppress degradation of crystal quality.
  • a p-AlGaN/p-InGaN superlattice structure is more preferable because p-InGaN exhibits superior crystal quality at a low growth temperature as compared with p-GaN.
  • Japanese Patent Application Laid-Open (kokai) No. 2005-51170 discloses that a superlattice structure in which p-AlGaN and p-InGaN are alternately deposited is used as a p cladding layer. It is also disclosed that p-AlGaN has a thickness of 1 nm to 5 nm and p-InGaN has a thickness of 1 nm to 5 nm.
  • Japanese Patent Application Laid-Open (kokai) No. 2007-80996 discloses that a superlattice structure in which p-AlGaN and p-GaN are alternately deposited is used as a p cladding layer. It is also disclosed that each of p-AlGaN and p-GaN has a thickness of at least one atomic layer.
  • an object of the present invention is to provide a method for producing a Group III nitride semiconductor light-emitting device without increasing the driving voltage.
  • a method for producing a Group III nitride semiconductor light-emitting device having a p cladding layer comprises forming a p cladding layer by repeatedly growing a p-AlGaN layer having a thickness of 0.5 nm to 10 nm and an InGaN layer by MOCVD, wherein the InGaN layer having a thickness of one to two monolayer is formed on the p-AlGaN layer by stopping the supply of an Al source gas, introducing an In source gas, and increasing the supply amount of a Ga source gas while maintaining the p-AlGaN layer at a growth temperature.
  • a method for producing a Group III nitride semiconductor light-emitting device having a p cladding layer comprises forming a p cladding layer by repeating a first process of growing a p-AlGaN layer having a thickness of 0.5 nm to 10 nm and a second process of exposing a surface of the p-AlGaN layer to gases for growing InGaN by stopping the supply of an Al source gas, introducing an In source gas, and increasing the supply amount of a Ga source gas while maintaining the p-AlGaN layer at a growth temperature.
  • Group IIIB Group 13
  • Group VB Group 15
  • Specific examples of the Group III nitride semiconductor include those containing at least Ga, such as GaN, InGaN, AlGaN, and AlGaInN.
  • TMA trimethylaluminum
  • TMI trimethylindium
  • TMG trimethylgallium
  • the thickness of one monolayer (or monomolecular layer, hereinafter the term of monolayer is used) of p-InGaN is half the lattice constant of c axis of p-InGaN, i.e., about 2.5 ⁇ to 2.6 ⁇ , depending on the In composition ratio.
  • the p-AlGaN layer has a thickness of 0.5 nm to 10 nm is as follows: when the thickness is smaller than 0.5 nm, the function as a p cladding layer, that is, the effect of electron confinement is degraded, which is not desirable. When the thickness is larger than 10 nm, the crystal quality of the p-AlGaN layer is degraded. More preferably, the p-AlGaN layer has a thickness of 1 nm to 5 nm, and further preferably, 1.5 nm to 3.5 nm.
  • the p-AlGaN layer and the InGaN layer are grown at a temperature of 800° C. to 950° C.
  • the growth temperature is within this range, the crystal quality of the p-AlGaN layer can be significantly improved by exposing the surface of the p-AlGaN layer to the gases for forming InGaN.
  • the growth temperature is more preferably, 830° C. to 920° C., and further preferably, 850° C. to 900° C.
  • the p-AlGaN layer has an Al composition ratio x of 15 mol % to 50 mol % when the p-AlGaN is defined as p-Al x Ga 1-x N. That is x is ratio of number of moles of Al to number of moles of Al and Ga. When the Al composition ratio is within this range, the effect of electron confinement by the p cladding layer can be significantly enhanced.
  • the Al composition ratio x is more preferably, 20 mol % to 40 mol %, and further preferably, 25 mol % to 35 mol %.
  • the InGaN layer preferably has an In composition ratio y of 2 mol % to 10 mol % when the InGaN is defined as In y Ga 1-y N. That is y is ratio of number of moles of In to number of moles of In and Ga. When the In composition ratio is within this range, the crystal quality of the p-AlGaN layer can be further improved by the InGaN layer.
  • the In composition ratio y is more preferably, 4 mol % to 8 mol %, and further preferably, 6 mol % to 8 mol %.
  • the InGaN layer may be a p-InGaN layer doped with Mg.
  • a second aspect of the present invention is drawn to a specific embodiment of the production method according to the first aspect, wherein the growth temperature of the p-AlGaN layer is 800° C. to 950° C.
  • a third aspect of the present invention is drawn to a specific embodiment of the production method according to the first or second aspect, wherein the p-AlGaN layer has an Al composition ratio x of 15 mol % to 50 mol %.
  • a fourth aspect of the present invention is drawn to a specific embodiment of the production method according to any of the first to third aspects, wherein the InGaN layer has an In composition ratio y of 2 mol % to 10 mol %.
  • a sixth aspect of the present invention is drawn to a specific embodiment of the production method according to the fifth aspect, wherein the p-AlGaN layer is grown at a temperature of 800° C. to 950° C.
  • a seventh aspect of the present invention is drawn to a specific embodiment of the production method according to the fifth or sixth aspect, wherein the p-AlGaN layer has an Al composition ratio x of 15 mol % to 50 mol %.
  • the thickness of the InGaN layer which does not contribute to electron confinement is reduced to one to two monolayers.
  • the crystal quality of the p-AlGaN layer is improved and the series resistance can be reduced, resulting in the reduction of the driving voltage.
  • the InGaN layer is grown at the same temperature as that of the p-AlGaN layer, and the supply amount of a Ga source gas when forming the InGaN layer is increased as compared with when forming the p-AlGaN layer. Thereby, the crystal quality of the p-AlGaN layer can be further improved by the InGaN layer.
  • the crystal quality of p-AlGaN can be improved by repeatedly exposing the surface of the p-AlGaN layer to the gases for forming InGaN although InGaN is not formed on the p-AlGaN layer. Since InGaN is not formed, the series resistance can be reduced, resulting in the reduction of the driving voltage.
  • FIG. 1 shows the configuration of a Group III nitride semiconductor light-emitting device according to Embodiment 1;
  • FIG. 2 shows the structure of a p cladding layer 15 ;
  • FIGS. 3A , 3 B, and 3 C show the process for producing the Group III nitride semiconductor light-emitting device according to Embodiment 1;
  • FIGS. 4A , 4 B, and 4 C show the process for producing a p cladding layer 25 according to Embodiment 2.
  • FIG. 1 shows the configuration of a Group III nitride semiconductor light-emitting device according to Embodiment 1.
  • the Group III nitride semiconductor light-emitting device according to Embodiment 1 includes a sapphire substrate 10 ; and an n contact layer 11 , an nESD layer 12 , an n cladding layer 13 , a light-emitting layer 14 , a p cladding layer 15 , and a p contact layer 16 , each of the layers being formed of Group III nitride semiconductor, are sequentially deposited on the substrate 10 via a low temperature buffer layer (not illustrated).
  • a trench having a depth extending from the top surface of the p contact layer 16 to the n contact layer 11 is formed in a portion of the top surface of the p contact layer 16 .
  • An n-electrode 19 is formed on the surface of the n-contact layer exposed at the bottom of the trench.
  • An ITO transparent electrode 17 is formed on a portion of the p contact layer 16 which has no trench, and a p-electrode 18 is formed on the transparent electrode 17 .
  • the p cladding layer 15 has a superlattice structure formed of layer units, each including a p-AlGaN layer 150 and a p-InGaN layer 151 , which are alternately deposited, as shown in FIG. 2 .
  • the number of layer units is 5 to 15.
  • the p-AlGaN layer 150 has a thickness of 0.5 nm to 10 nm, an Al composition ratio of 15 mol % to 50 mol %, and a Mg concentration of 1 ⁇ 10 19 /cm 3 to 5 ⁇ 10 20 /cm 3 .
  • the p-InGaN layer 151 has a thickness of one to two monolayer, an In composition ratio of 2 mol % to 10 mol %, and a Mg concentration of 1 ⁇ 10 19 /cm 3 to 2 ⁇ 10 20 /cm 3 .
  • the thickness of one monolayer of InGaN is half the lattice constant of c axis of InGaN, i.e., about 2.5 ⁇ to 2.6 ⁇ , depending on the In composition ratio.
  • the overall thickness of the p cladding layer 15 is 10 nm to 90 nm.
  • Layers other than the p cladding layer 15 may have any conventionally known structure.
  • the n contact layer 11 being formed of n-GaN may comprise a plurality of layers having different Si contents.
  • the nESD layer 12 has a two-layer structure including an i-GaN layer and an n-GaN layer.
  • the n cladding layer 13 has a superlattice structure in which i-GaN and i-InGaN are alternately and repeatedly formed.
  • the light-emitting layer 14 has a MQW structure in which an undoped InGaN well layer and an undoped GaN barrier layer are alternately deposited three times.
  • the p contact layer 16 being formed of p-GaN may comprise a plurality of layers having different Mg contents.
  • the p-type Group III nitride semiconductor is actually produced by heat treatment of Mg doped Group III nitride semiconductor in the subsequent process. However, hereinafter, for simplification, it is referred to as p-AlGaN or p-InGaN even before heat treatment.
  • the sapphire substrate 10 on the surface of which the concave and convex are formed is placed in an MOCVD apparatus, and heated in a hydrogen atmosphere for thermal cleaning.
  • a low temperature buffer layer (not illustrated) is formed on the sapphire substrate 10 .
  • An n contact layer 11 , an nESD layer 12 , an n cladding layer 13 , and a light-emitting layer 14 are sequentially formed on the low temperature buffer layer by MOCVD ( FIG. 3A ).
  • the gases employed are as follows: hydrogen or nitrogen as a carrier gas; ammonia gas as a nitrogen source; TMG (trimethylgallium) as a Ga source; TMA (trimethylaluminum) as an Al source; TMI (trimethylindium) as an In source; and silane (SiH 4 ) as an n-type dopant gas.
  • a p cladding layer 15 is formed through the following processes.
  • a p-AlGaN layer 150 having a thickness of 0.5 nm to 10 nm, an Al composition ratio of 15 mol % to 50 mol %, and a Mg concentration of 1 ⁇ 10 19 /cm 3 to 5 ⁇ 10 20 /cm 3 .
  • the same carrier gas and raw material gases as mentioned above are employed.
  • Biscyclopentadienylmagnesium (Mg(C 5 H 5 ) 2 ) is used as a p-type dopant gas.
  • the growth temperature is 800° C. to 950° C.
  • a p-InGaN layer 151 having a thickness of one to two monolayer, an In composition ratio of 2 mol % to 10 mol %, and an Mg concentration of 1 ⁇ 10 19 /cm 3 to 2 ⁇ 10 20 /cm 3 .
  • a p cladding layer 15 having a p-AlGaN/p-InGaN superlattice structure is formed by alternately repeating the process of forming the p-AlGaN layer 150 and the process of forming the p-InGaN layer 151 five to fifteen times so that these layers are alternately deposited ( FIG. 3B ).
  • a part or whole of the p-InGaN layer 151 may be lost due to evaporation during switching to the gases for forming the p-AlGaN layer 150 on the p-InGaN layer 151 , or at the initial growth stage of the p-A GaN layer 150 .
  • the reason that the p-AlGaN layer 150 is grown at a low temperature of 800° C. to 950° C. in forming the p cladding layer 15 is to reduce thermal damage to the light-emitting layer 14 .
  • the p-AlGaN layer 150 is grown at a low temperature, the growth is more promoted in the longitudinal direction than in the lateral direction. The layer surface is easily roughened, resulting in degradation of crystal quality. Therefore, the p-InGaN layer 151 exhibiting enhanced growth in the lateral direction and good crystal quality even at a low temperature is used to form a superlattice structure.
  • the p-AlGaN layer 150 has a thickness of 0.5 nm to 10 nm to suppress degradation of crystallinity.
  • the p-InGaN layer 151 has a thickness of one to two monolayer to minimize the thickness of the p-InGaN layer 151 which does not function as a cladding layer serving to confine electrons in the light-emitting layer 14 .
  • the supply amount of TMG as a Ga source is increased in forming the p-InGaN layer 151 , thereby preventing evaporation of In and further improving the crystal quality of the p-AlGaN layer 150 by the p-InGaN layer 151 .
  • the p-InGaN layer 151 is thinned, and the overall thickness of the p cladding layer 15 is reduced. As a result, the series resistance of the p cladding layer 15 is reduced, thereby reducing the driving voltage of the Group III nitride semiconductor light-emitting device.
  • the p-AlGaN layer 150 has more preferably a thickness of 1 nm to 5 nm to enhance the function as a cladding layer and the crystal quality. Further preferably, the thickness is 1.5 nm to 3.5 nm.
  • the p-AlGaN layer 150 has an Al composition ratio of 20 mol % to 40 mol % to enhance the function as a cladding layer. Further preferably, the Al composition ratio is 25 mol % to 35 mol %.
  • the p-InGaN layer 151 has an In composition ratio of 4 mol % to 8 mol % to enhance the crystal quality of the p-AlGaN layer 150 by the p-InGaN layer 151 . Further preferably, the In composition ratio is 6 mol % to 8 mol %.
  • the p-InGaN layer 151 may be replaced with the InGaN layer which is undoped with the p-type dopant.
  • the p-AlGaN layer 150 and the p-InGaN layer 151 are more preferably grown at a temperature of 830° C. to 920° C. to enhance the crystal quality of the p-AlGaN layer 150 by the p-InGaN layer 151 . Further preferably, the growth temperature is 850° C. to 900° C.
  • a p contact layer 16 is formed by MOCVD ( FIG. 3C ).
  • the same raw material gases, carrier gas, and doping gas are employed as those when the p cladding layer 15 was formed.
  • a transparent electrode 17 is formed in a portion of the p contact layer 16 .
  • a trench having a depth reaching the n contact layer 11 is formed in a portion other than the transparent electrode 17 of the surface of the p contact layer 16 .
  • An n-electrode 19 is formed at the bottom of the trench, and a p-electrode 18 is formed on the transparent electrode 17 .
  • a p-AlGaN layer 250 having a thickness of 0.5 nm to 10 nm, an Al composition ratio of 15 mol % to 50 mol %, and a Mg concentration of 1 ⁇ 10 19 /cm 3 to 5 ⁇ 10 20 /cm 3 ( FIG. 4A ).
  • the growth temperature is 800° C. to 950° C.
  • the supply of TMA is stopped, TMI is introduced and the supply amount of TMG is increased.
  • the surface of the p-AlGaN layer 250 is exposed to the gases for forming InGaN. This process is finished before InGaN is formed on the p-AlGaN layer 250 , and the process of forming the p-AlGaN layer 250 is performed again ( FIG. 4B ).
  • the process of forming the p-AlGaN layer 250 and the process of exposing the surface of the p-AlGaN layer 250 to the gases for forming InGaN are alternately repeated five to fifteen times to form a p cladding layer 25 as shown in FIG. 4C .
  • the above mentioned process of forming the p cladding layer 25 can suppress degradation of crystallinity because the surface of the p-AlGaN layer 250 is recovered by exposure to the gases for forming InGaN. While maintaining good crystal quality of the p-AlGaN layer 250 , the overall thickness of the p cladding layer 25 is reduced because InGaN is not formed. As a result, the series resistance of the p cladding layer 25 is reduced, thereby reducing the driving voltage of the Group III nitride semiconductor light-emitting device.
  • the Group III nitride semiconductor light-emitting device according to Embodiments 1 and 2 have a face-up-type structure
  • the light-emitting device of the present invention may have a flip-chip-type structure.
  • the Group III nitride semiconductor light-emitting device produced by the method of the present invention can be employed as a light source of an illumination apparatus, or a display apparatus.

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CN112802936B (zh) * 2020-12-30 2023-07-28 山西中科潞安紫外光电科技有限公司 一种复合型pAlGaN电极接触层、深紫外LED外延片及其制备方法
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